CN114591224A - 一种具备水合物抑制功能的缓蚀剂及其制备方法和应用 - Google Patents
一种具备水合物抑制功能的缓蚀剂及其制备方法和应用 Download PDFInfo
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- CN114591224A CN114591224A CN202011396933.9A CN202011396933A CN114591224A CN 114591224 A CN114591224 A CN 114591224A CN 202011396933 A CN202011396933 A CN 202011396933A CN 114591224 A CN114591224 A CN 114591224A
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- Prior art keywords
- pyridine
- compound
- bipyridine
- corrosion inhibitor
- halogenated
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- 238000005260 corrosion Methods 0.000 title claims abstract description 75
- 230000007797 corrosion Effects 0.000 title claims abstract description 74
- 239000003112 inhibitor Substances 0.000 title claims abstract description 56
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 halogenated pyridine quaternary ammonium salt Chemical class 0.000 claims abstract description 57
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 27
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 26
- 150000008282 halocarbons Chemical class 0.000 claims description 22
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 17
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 150000003222 pyridines Chemical class 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011630 iodine Chemical group 0.000 claims description 6
- 229910052740 iodine Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
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- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 10
- 239000010959 steel Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004781 supercooling Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229960004011 methenamine Drugs 0.000 description 5
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000010962 carbon steel Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000010779 crude oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明提供了一种具备水合物抑制功能的缓蚀剂及其制备方法和应用。所述缓蚀剂包括如下质量百分比的组分:1‑30%卤化吡啶季铵盐、55‑94%溶剂和0.1%‑15%助剂。本发明制备的缓蚀剂可同时实现钢质管线设备内腐蚀防护和水合物抑制功能,并且同时相比同类技术具备制备简便的优点;该缓蚀剂在10‑60℃、H2S‑CO2‑Cl‑环境下对20#钢材质腐蚀的缓蚀率高于90%,同时过冷度大于6℃。
Description
技术领域
本发明涉及石油及天然气管道防腐防堵领域,具体涉及一种具备水合物抑制功能的缓蚀剂及其制备方法和应用。
背景技术
在酸性气体、液体通过金属管道的运输过程中,例如酸性天然气输送至天然气净化厂过程中,安全平稳是最为基本的要求。其中,管道腐蚀损坏对安全产生影响,水合物堵塞对平稳运行产生影响。针对管道腐蚀,添加缓蚀剂是常用的一类抑制金属管道腐蚀的方法,能够延长管道的使用寿命;针对水合物堵塞,添加水合物抑制剂是常用的方法。
目前,在酸性天然气输送过程中,主要通过分别加注缓蚀剂和水合物抑制剂来实现抑制腐蚀和抑制水合物,而具备抑制水合物功能的缓蚀剂报道较少。如CN101666427B报道了一种含有缓蚀剂的高效水合物抑制剂,在不含硫化氢二氧化碳的原油环境中可以抑制水合物和碳钢腐蚀;CN107936921A通过七步反应合成了一种防腐防冰堵双功能化学添加剂,可以抑制水合物和碳钢腐蚀;RU2661635C1报道了氯化二丁基二(2-(1-氯)烯丙基)季铵盐的合成方法,该化合物兼具抑制水合物、防腐功能,但是合成中需要无水环境,且需要4个步骤以上;US2004167040A1和US2009173663A报道了两种琥珀酸衍生物的分子结构,针对油水(油:水=1:9,水中含有5%氯化钠)环境可以抑制碳钢腐蚀。
此外,含硫化氢气田腐蚀和水合物堵塞问题更为严重,但是前期报道几乎没有涉及含硫气田环境;同时,制备过程也相对复杂,对制备过程控制要求较高,因此,现有技术中亟需寻找同时能达到石油天然气管道防腐防堵目的的试剂。
发明内容
为了解决上述问题,本发明的目的在于提供一种具备水合物抑制功能的缓蚀剂,该缓蚀剂可同时实现钢质管线设备内腐蚀防护和水合物抑制功能。
本发明的另一个目的在于提供一种上述具备水合物抑制功能的缓蚀剂的制备方法。
本发明的再一个目的在于提供上述具备水合物抑制功能的缓蚀剂的应用。
为达上述目的,本发明提供了一种卤化吡啶季铵盐,其是通过包括如下的制备方法制备而成:将联吡啶类化合物、吡啶类化合物和卤代烃加入到溶剂中充分混合后进行反应,即得;其中,联吡啶类化合物选自4,4-联吡啶及其衍生物、2,2-联吡啶及其衍生物中的任意一种;所述吡啶类化合物选自吡啶和2,6-二甲基吡啶中的任意一种,所述卤代烃的结构式为:X-R6-X,R6选自碳原子数为1-20的烷基、环烷基、芳基、烷基芳基和烯基;X选自氟、氯、溴和碘。
根据本发明的一些具体实施方案,所述联吡啶类化合物选自4,4-联吡啶和2,2-联吡啶中的任意一种,优选为4,4-联吡啶。
根据本发明的一些具体实施方案,所述吡啶类化合物选自2,6-二甲基吡啶。
根据本发明的一些具体实施方案,所述R6选自碳原子数为1-20的芳基和烷基芳基;X选自氯、溴和碘。
根据本发明的一些具体实施方案,所述卤代烃包括联苯二氯苄。
根据本发明的一些具体实施方案,所述溶剂选自甲醇、乙醇、乙二醇、二甘醇和三甘醇中的一种或两种以上的组合。
根据本发明的一些具体实施方案,所述联吡啶类化合物、吡啶类化合物、卤代烃和溶剂共同组成一个反应体系,该反应体系中所述联吡啶类化合物、吡啶类化合物和卤代烃的摩尔比为(0.3-1):(0.5-1.5):(0.5-1.5),所述溶剂占所述反应体系的质量百分比为55-94%,优选为80-90%。
另一方面,本发明还提供了一种具备水合物抑制功能的缓蚀剂,所述缓蚀剂包括上述卤化吡啶季铵盐。
根据本发明的一些具体实施方案,所述缓蚀剂包括如下质量百分比的组分:1-30%卤化吡啶季铵盐、55-94%溶剂和0.1-15%助剂,优选为如下质量百分比的组分:1-24%卤化吡啶季铵盐、75-94%溶剂和0.1-10%助剂,进一步优选为如下质量百分比的组分:8-15%卤化吡啶季铵盐、80-90%溶剂和1-5%助剂。
根据本发明的一些具体实施方案,所述溶剂选自甲醇、乙醇、乙二醇、二甘醇和三甘醇中的一种或两种以上的组合。
根据本发明的一些具体实施方案,所述助剂选自含氮化合物、含硫化合物和无机盐中的一种或两种以上的组合。
根据本发明的一些具体实施方案,所述含氮化合物选自六次甲基四胺、三氮唑、苯骈三氮唑、咪唑、咪唑啉、甲基咪唑、N-甲基咪唑、嘧啶、吡嗪、哒嗪、吲哚、三嗪、碳原子数为1-20的烷基胺和芳基胺中的一种或两种以上的组合。
根据本发明的一些具体实施方案,所述含硫化合物选自硫脲、噻吩、噻唑和苯并噻唑中的一种或两种以上的组合。
根据本发明的一些具体实施方案,所述无机盐选自碘化钾、碘化钠、钼酸盐、钨酸盐和铬酸盐中的一种或两种以上的组合。
另一方面,本发明还提供了上述缓蚀剂的制备方法,所述制备方法包括以下步骤:将联吡啶类化合物、吡啶类化合物和卤代烃加入到溶剂中充分混合后进行反应,反应结束后再向体系中加入助剂并混合均匀,得到所述缓蚀剂。
根据本发明的一些具体实施方案,所述联吡啶类化合物的结构式为:
其中,R7选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R8选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R9选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R10选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R11选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;其中,R12选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R13选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R14选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基。
根据本发明的一些具体实施方案,所述吡啶类化合物的结构式为:
其中,R1选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R2选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R3选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R4选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基;R5选自H或碳原子数为1-20的烷基、环烷基、芳基、烷基芳基、烯基。
根据本发明的一些具体实施方案,所述联吡啶类化合物选自4,4-联吡啶及其衍生物、2,2-联吡啶及其衍生物的任意一种,优选为4,4-联吡啶;吡啶类化合物选自吡啶和2,6-二甲基吡啶中的任意一种,优选为2,6-二甲基吡啶。
根据本发明的一些具体实施方案,所述卤代烃的结构式为:X-R6-X,其中,R6选自碳原子数为1-20的烷基、环烷基、芳基、烷基芳基和烯基,优选自芳基和烷基芳基;X选自氟、氯、溴、碘,优选自氯、溴和碘。
根据本发明的一些具体实施方案,所述卤代烃包括联苯二氯苄。
根据本发明的一些具体实施方案,所述联吡啶类化合物、吡啶类化合物和卤代烃的摩尔比为(0.3-1):(0.5-1.5):(0.5-1.5)。
根据本发明的一些具体实施方案,所述联吡啶类化合物、吡啶类化合物和卤代烃混合后进行反应温度为40-120℃。
根据本发明的一些具体实施方案,所述联吡啶类化合物、吡啶类化合物和卤代烃混合后进行反应的时间为0.5-24小时。
再一方面,本发明还提供了上述缓蚀剂在含硫气田腐蚀和水合物堵塞中的应用。
本发明的有益效果:
本发明制备的缓蚀剂可同时实现钢质管线设备内腐蚀防护和水合物抑制功能,并且同时相比同类技术具备制备简便的优点;该缓蚀剂在10-60℃、H2S-CO2-Cl-环境下对20#钢材质腐蚀的缓蚀率高于90%,同时过冷度优于单独使用乙二醇。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解,现对本发明/的技术方案进行以下详细说明,但不能理解为对本发明的可实施范围的限定。
标气,组成见表1,四川歌瑞标准物质科技有限公司。
表1
另外在以下具体实施例中,所涉及的操作未注明条件者,均按照常规条件或者制造商建议的条件进行。所用原料未注明生产厂商及规格者均为可以通过市购获得的常规产品。
实施例1
本实施例提供了一种缓蚀剂的制备方法,具体如下:
将1摩尔吡啶、1摩尔联苯二氯苄、0.5摩尔4,4-联吡啶和3000克乙二醇加入烧瓶中,安装搅拌器,温度计以及回流冷凝管。在搅拌情况下加热至80℃,反应6小时停止反应,得到卤化吡啶季铵盐体系,待冷却至室温后进一步加入六次甲基四胺105克,即得到最终缓蚀剂,该缓蚀剂中包含如下质量百分比的组分:卤化吡啶季铵盐11.6%,乙二醇85.4%,六次甲基四胺3%。
实施例2
本实施例提供了一种缓蚀剂的制备方法,具体如下:
将1摩尔2,6-二甲基吡啶、1摩尔联苯二氯苄、0.5摩尔4,4-联吡啶和3000克乙二醇加入烧瓶中,安装搅拌器,温度计以及回流冷凝管。在搅拌情况下加热至100℃,反应6小时停止反应,得到卤化吡啶季铵盐体系,待冷却至室温后进一步加入六次甲基四胺105克,即得到最终缓蚀剂,该缓蚀剂中包含如下质量百分比的组分:卤化吡啶季铵盐12%,乙二醇85%,六次甲基四胺3%。
实施例3
本实施例将通过实施例1和实施例2得到的缓蚀剂的应用进行缓蚀性能评价(参考评价标准SY/T 5273),并将没有使用缓蚀剂的作为对比例(空白)。该缓蚀性能评价条件为:NaCl:5%,H2S:1480ppm,CO2:288ppm,通过实施例1和实施例2得到缓蚀剂,缓蚀剂的添加浓度为200ppm,实验温度为40℃,实验时间为72小时,实验应用的材质为20#钢,即含碳量为0.2%的钢。缓蚀剂缓蚀性能评价结果在表2中示出。
表2
实验材质 | 失重(mg)( | 缓蚀率(%) | |
空白 | 20#钢 | 36.9 | —— |
实例1缓蚀剂 | 20#钢 | 2.8 | 92.4 |
实例2缓蚀剂 | 20#钢 | 2.1 | 94.3 |
从表1中可以看出,通过制备实施例1和实施例2得到的缓蚀剂的缓蚀率均超过90%,能有效抑制H2S-CO2-Cl-环境中碳钢的腐蚀。
实施例4
本实施例将通过添加实施例2得到的缓蚀剂对水合物生成温度的试验,并采用去离子水作为对比例。实验过程为:将实施例2缓蚀剂与去离子水混合均匀得到10%的缓蚀剂溶液作为实验溶液。将该实验溶液置于具备蓝宝石观察窗的高压设备中并通入标气使体系总压力达到7MPa;保持总压力不变的条件下逐步降温,观察并记录水合物形成温度。同时,分别以去离子水和加入10%乙二醇的去离子水作为实验溶液在同样条件下开展实验作为对比例。水合物生成温度结果在表3中示出。
表3
水合物形成温度(℃) | |
去离子水 | 18.8 |
10%缓蚀剂溶液 | 10.3 |
乙二醇 | 11.5 |
通过表3中的结果可以看出,添加制备实施例2得到的缓蚀剂后,溶液水合物形成温度由18.8℃降低至10.3℃,作为对比的乙二醇则降为11.5℃,说明通过本发明实施例提供的缓蚀剂具有水合物抑制功能,且抑制效果优于乙二醇,可以应用于酸性天然气的运输金属管线,能有效抑制水合物的产生。
上述所有可选技术方案,可以采用任意结合形成本发明的可选实施例,在此不再一一赘述。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (21)
1.一种卤化吡啶季铵盐,其是通过包括如下的制备方法制备而成:
将联吡啶类化合物、吡啶类化合物和卤代烃加入到溶剂中充分混合后进行反应,即得;
其中,所述联吡啶类化合物选自4,4-联吡啶及其衍生物、2,2-联吡啶及其衍生物中的任意一种,吡啶类化合物选自吡啶和2,6-二甲基吡啶中的任意一种,所述卤代烃的结构式为:X-R6-X,R6选自碳原子数为1-20的烷基、环烷基、芳基、烷基芳基和烯基;X选自氟、氯、溴和碘。
2.根据权利要求1所述的卤化吡啶季铵盐,其中,所述联吡啶类化合物选自4,4-联吡啶和2,2-联吡啶中的任意一种,优选为4,4-联吡啶;所述吡啶类化合物选自2,6-二甲基吡啶。
3.根据权利要求1或2所述的卤化吡啶季铵盐,其中,所述R6选自碳原子数为1-20的芳基和烷基芳基;X选自氯、溴和碘。
4.根据权利要求1-3任一项所述的卤化吡啶季铵盐,其中,所述卤代烃包括联苯二氯苄。
5.根据权利要求1-4中任一项所述的卤化吡啶季铵盐,其中,所述溶剂选自甲醇、乙醇、乙二醇、二甘醇和三甘醇中的一种或两种以上的组合。
6.根据权利要求1-5任一项所述的卤化吡啶季铵盐,其中,所述联吡啶类化合物、吡啶类化合物、卤代烃和溶剂共同组成一个反应体系,该反应体系中所述联吡啶类化合物、吡啶类化合物和卤代烃的摩尔比为(0.3-1):(0.5-1.5):(0.5-1.5),所述溶剂占所述反应体系的质量百分比为55-94%,优选为80-90%。
7.一种具备水合物抑制功能的缓蚀剂,其中,所述缓蚀剂包括权利要求1-6任一项所述的卤化吡啶季铵盐。
8.根据权利要求7所述的缓蚀剂,其中,所述缓蚀剂包括如下质量百分比的组分:1-30%卤化吡啶季铵盐、55-94%溶剂和0.1%-15%助剂,优选为如下质量百分比的组分:1-24%卤化吡啶季铵盐、75-94%溶剂和0.1-10%助剂,进一步优选为如下质量百分比的组分:8-15%卤化吡啶季铵盐、80-90%溶剂和1-5%助剂。
9.根据权利要求8所述的缓蚀剂,其中,所述溶剂选自甲醇、乙醇、乙二醇、二甘醇和三甘醇中的一种或两种以上的组合。
10.根据权利要求8或9所述的缓蚀剂,其中,所述助剂选自含氮化合物、含硫化合物和无机盐中的一种或两种以上的组合。
11.根据权利要求10所述的缓蚀剂,其中,所述含氮化合物选自六次甲基四胺、三氮唑、苯骈三氮唑、咪唑、咪唑啉、甲基咪唑、N-甲基咪唑、嘧啶、吡嗪、哒嗪、吲哚、三嗪、碳原子数为1-20的烷基胺和芳基胺中的一种或两种以上的组合。
12.根据权利要求10所述的缓蚀剂,其中,所述含硫化合物选自硫脲、噻吩、噻唑和苯并噻唑中的一种或两种以上的组合。
13.根据权利要求10-12任一项所述的缓蚀剂,其中,所述无机盐选自碘化钾、碘化钠、钼酸盐、钨酸盐和铬酸盐中的一种或两种以上的组合。
14.权利要求7-13中任一项所述的缓蚀剂的制备方法,其中,所述制备方法包括以下步骤:
将联吡啶类化合物、吡啶类化合物和卤代烃加入到溶剂中充分混合后进行反应,反应结束后再向体系中加入助剂并混合均匀,得到所述缓蚀剂。
15.根据权利要求14所述的制备方法,其中,所述联吡啶类化合物选自4,4-联吡啶及其衍生物、2,2-联吡啶及其衍生物中的任意一种,优选为4,4-联吡啶;所述吡啶类化合物选自吡啶和2,6-二甲基吡啶中的任意一种,优选为2,6-二甲基吡啶。
16.根据权利要求14所述的制备方法,其中,所述卤代烃的结构式为:X-R6-X,其中,R6选自碳原子数为1-20的烷基、环烷基、芳基、烷基芳基和烯基,优选自芳基和烷基芳基;X选自氟、氯、溴、碘,优选自氯、溴和碘。
17.根据权利要求14所述的制备方法,其中,所述卤代烃包括联苯二氯苄。
18.根据权利要求14所述的制备方法,其中,所述联吡啶类化合物、吡啶类化合物和卤代烃的摩尔比为(0.3-1):(0.5-1.5):(0.5-1.5)。
19.根据权利要求14所述的制备方法,其中,所述联吡啶类化合物、吡啶类化合物和卤代烃混合后进行反应温度为40-120℃。
20.根据权利要求14-19任一项所述的制备方法,其中,所述联吡啶类化合物、吡啶类化合物和卤代烃混合后进行反应的时间为0.5-24小时。
21.权利要求1-6任一项所述的卤化吡啶季铵盐或权利要求7-13任一项所述的缓蚀剂在含硫气田腐蚀和水合物堵塞中的应用。
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CN117143332B (zh) * | 2023-10-27 | 2024-01-02 | 东营市百扬石油科技有限责任公司 | 一种用于含硫酸盐还原菌油田污水的缓蚀剂的制备方法 |
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